Production of black upon textile fibers.



UNITED STATES EMILE AUGUSTE FOUBNEAUX, OF MANCHESTER, ENGLAND.

PRODUCTION 0]? BLACK UPON TEXTILE FIBER/S.

No Drawing.

To all-whom it may concern:

Be it known that I, EMILE AUGUSTE Foun- NEAUX, a subject of the King of Great Britain, ,residing at St. J amess Buildings, Oxford street, Manchester, in the county of Lancaster, England, have invented new and useful Improvements in the Production of Black upon Textile Fibers, of which the following is a specification.

My invention relates to improvements in the production of anilin black upon vegetable textile fibers. I

The known processes for the production of ungreenable'anilin blacks having little or no tendering effect on the fiber do not appear to have proved entirely satisfactory in practice.

a A number of them depend on after treatments, such as chroming, frequentl in the presence of anilin, which load the fi er with mineral matter and are particularl objectionable if the black is to be app ied for printing purposes or for discharge purposes, as they have a detrimental efieet on the whites.

Other processes uire special precautions in drying and aging and in some cases the necessary precautions can onl be carried out by means of special an complicated apparatus. In many cases the results 7 obtained when following the indications given in the specifications fall short of technical requirements.

After an extensive research I have succeeded in devising a recess for the production of an ungreenable anilin black which has little or no tendering eflect on the fiber, which does not require any after treatment whatever except washing andsoapin and which can be carried out with the or mary machinery generally available in every print works, to wit, a padding mangle, a set of drying cans, a short steamer or anilin ager of the Mather and Platt type and the necessarry washing and soaping machinery.

he new process is an improvementon the process of the previous British Patentllo'. 7345 of 1908 granted jointly to The Calico Printers Association Limited and myself.'

The said patented process was based on the discovery that anilin black mixtures con taining not more than one molecular proportion of a strong mineral acid for three molecular proportions of anilin do not tender the fiber very materially provided they are of such composition as to lead to the Specification of Letters Patent.

Patented Aug. 27. 1918.

Application filed August 9, 1917. -Serial No. 185,288.

rapid and smooth formation of ungreenable black under the conditions of development. In that patent it was assumed that under conditions favoring the rapid and smooth formation of ungreenable anilin black the oxids of chlorin roduced from the chlorate by the action 0 the catalytic agent affect the bases by selective action in preference to the fiber, while under the opposite conditions the 'oxids ofchlorin not bein readily taken up by the bases attack the her and under such unsuitable conditions form a materially larger proportion of oxycellulose than is formed in the application of the ordinary oxidation black.

My present process differs from the process of the previous British Patent No. 7345 of 1908 in the following particulars 1. I am now able to dispense with the use of metallic salts with an acid function, which was found undesirable in practice.

2. The proportion of organic catalytic agent required has been very materially reduced. V I

3. I now use boracic acid for the purpose of preventing undue loss of anilin in dry- 1n I now use cop er salts as mineral catalytic agents in re erence to vanadium salts.

These alteratlons have resulted in a very material improvement in the shade andfastness of the black, in the working ualities of the mixtures, (padding liquors an printing colors) and in a further material reduction of the danger of tenderin In carrying my invention into e ect I use mixtures consisting of.

(a) Anilin alone, or in admixture with other primary amins of the benzene series, (but not ammodiphenylamin compounds,) provided always that the proportion of amins substituted in para position in relation to the amino grou does not exceed three molecular proportions out of a total of eleven molecular proportions of amins.

(b) A strong mineral acid used in such proportions as not to interfere materially with the condensation of the intermediary products of the nigranilin type with anilin to un reenable anilin blacks. The acids best suit'ef for my purpose are hydrochloric acid and nitric acid.

(c) Formic' acid in such proportion as may be required jointly with themineral acid to prevent the formation of any material amount of undesirable brown bvsalts, preferably copper sulfid.

products. For paddin purposes formic acig may be partly su stituted by lactic aci (d) A suitable thickening and- (e) Boracic acid for the purpose of preventing any undue loss of anilin during the drying operation and of retaining a proportion of amin sufiicient to convert all the intermediary products of the nigranilin t pe formed into ungreenable anilin blacks.- T e boracic acid may be part1 substituted by the phoisphoric acids, preferably metaphosp oric ac1 (f) Chlorates of the alkali metals as oxidizing agents.

.(g) An organic catalytic agent, preferably paraphenylene diamin, which may hlowever be substituted by its known equiva ents.

(h) A mineral catalytic agent, for padding piprposes preferably a soluble copper salt. or printing purposes insoluble copper ('11) For paddingpurposes the addition of lactic acid to the mixture has proved advantageous.

I am aware that the foregoing substances have been used in various mixtures for the production of anilin black and I wish it to be-clearly understood that my invention is characterized by their application in such combinations and proportions that under the working conditions hereinafter specified the oxidation takes place rapidly, smoothly and completely, and that the resulting ungreenable anilin black is immediately practically free of the unstable intermediary products. The actual proportions of the constituents vary according to their nature and to other circumstances and for this rea n I propose to give four typical mixtur -under Examples 1-4, to state to what extent these mixtures ma be modified without materially affecting the results obtained and to illustrate such modifications by Examples 5 to 8.

Examples 1 and 2 are typical of mixtures containin monoamins only. Examples 3 and 4 of mixtures containing monoamins and diamins other than paraphenylenedi- I amin which is common to all the mixtures.

Examples 1 and 2 are mixtures for padding purposes. ,Examples 3 and 4 mixtures for printin urposes.

The 0 lowing modifications are permissible:

1. The substances used may be substituted by their known equivalents as specified a ove Such substitutions may. in some cases imply a slight modification of the proportions of the substances used.

2. An alteration in the proportion of one of the constituents may to some extent be counterbalanced by a corresponding alteration in others.

mation of the interme iary products of the nigranilin series and their virtually complete condensation with primary amins to products of the ungreenable anilin black series takes place in one operation, the effect of the partial substitution of anilin by other bases is frequently much more pronounced than the effect of a similar substitution in ordinary anilin black mixtures Such substitutions lead to useful results in a number of cases. Thus the use of dianisidin in connection with anilin, as illustrated by Examples 3'and 4, leads to very dense and very ungreenable blacks. Benzidin and tolidin give similar but somewhat browner shades of black. The partial substitution of anilin by the chloranilins, preferably orthochloranilin, leads to materially increased fastness to chlorin of the resulting black. The substitution of other soluble copper salts for the copper chlorid used in the examples is practica le, but the use of copper sulfate involves a slight reduction an the use of copper salts of weak acids a corresponding increase in the proportion of mineral acid. Similar alterations are necessary when substituting the copper sulfid by other insoluble copper salts. enerally speaking such substitutions are not beneficial. The use of mineral catalytic agents other than copper salts is possible, but on the whole detrimental.

With regard to (2): Aireduction in the proportion of the mineral catalytic agent used may be compensated by a. corresponding increase in the proportion of'the organic catalytic agent, a reduction in the proportion of both catalytic agents by-an mcrease in the proportion of chlorate, but such alterations areonly permissible within relativel narrow limits.

lVith regardto(3) Aslight increase in the proportion of strong mineral acid leads to bluer, if somewhat-more greenable shades without necessarily increasing the danger of tendering very materially, especially if the proportion of chlorate be-shghtly reduced simultaneously. Any considerable increase in the proportion of stron mineral acid leads to greenable and tendering blacks, any material reduction in the proportion of strong mineral acid leads to dense' but brownish blacksl The pro ortion of boracic acid may be materially re need without any detrimental effect provided the material impregnated with the black mixture be dried at lower temperatures 1'. e. drying by hot air instead of can drying. Except as speciemon T fied above, any considerable alteration in the proportion of chlorate has a detrimental efl'ect. The same remark applies to the proportions of the catalytic agents, though in this case the mar 'n is somewhat wider.

- .These anilin b ack mixturesare a lied to the fabric or fiber by printin pa 'ng,

l .or otherwise impregnating, then rying and dred and seventy, anilin seventy four" and" 1 developing by steamin in a short steamer or anilin a er of the Matfier & Platt type. The materia blacks may be steamed after a mg if reuired and they are capable 0 being resisted by alkalin and reducing agents.

By using dilute black mixtures useful gray's may be produced. a

Ewamples.

Example No. 1parts' by weight Starch thirty-five, gum dragon mucilage'one hunone quarter, hydrochloric acid (thirty two chloric'acid (thlrty two degrees Twa dell) thirty nine and one-half, paraphen lene diamin h drochlorid four and one-half, formic acid ninety per cent. forty, boracic acid thirty four, sodium ch orate forty one, copper sulfid paste (twenty four per cent.) orty. Water to bulk to one thousand arts. Example No. 3-, arts by wei ht: nilin forty three and onealf, dianisi in nineteen and one-half, hydrochloric acid (thirt two degrees Twaddell), twenty four an one quarter, paraphenylene diamin hydrochlorid one and three quarters,'formic acid (ninety and one-half, coppersulfid paste per cent.) sixty five, lactic acid (thirty per cent.) thirty, boracic acid three, sodium chlorate twenty eight and one quarter, copper chlorid seven and three uarters. Thicken as required. Water to bul to one thousand arts.

Exam e No. I -parts by weight: Starch one hun' red, gum dragon mucilage one hundred, British gum seventy, anilin fifty-eight and three quarters, h drochloric acid (thirty two degreesTwadde l) fifty, araphenylene diamin hydrochlorid four an one-half, formic acid (ninety per cent.) forty, boracic acid eighteen,sod1um chlorate fort three twenty four per cent.) forty. Water to bulk to one thousand. a

Example No. 5--parts by weight; Anilin is then washed and soaped. The

severity, hydrochloric acid (thirty two degres Twaddell) twent three and.oneuar- 'ami-n. hydroch orid' three, formic acid (ninety per cent.) ninety, lactic acid (thirty percent.) forty eight, boracic acid forty, sodium chlorate forty ter, paraphenylene four undone-half, copper chlorid twelve and one-quarter. Thicken as required. Water to bulk to one thousand parts.

Example No. 6parts by weighti Anilin seventy four and one quarter, hydrochloric acid (thirty two degrees Twaddell) eighteen, paraphenylene diamin hydrochlorid three,

formic acid (ninety per cent.) ninety lactic acid (thirty per cent.) forty eight, meta hosphoric acid twelve and three-quarters,

oracic acid twenty, sodium chlorate forty eight, copper chlorid eleven. Thicken as required. Water to bulk to one thousand parts. 7 y 1 Example No. 7parts by weight: Starch eighty five, gum dragon mucilage three hundred and fifty, anilin sixty two and onequarter, hydrochloric acid (thirty two degrees Twaddell) forty and one-half, paraphenylene diamin hydrochlorid four and one-half, formic acid (ninety per cent.) forty, boracic. acid twenty five, sodium chlorate forty one, copper sulfid paste (twenty four per cent.) forty. Water to bulk to one thousand parts. I

Example No, 8parts by weight: Starch ninety, British gum eighty, anilin ninety two and one half, hydrochloric acid (thirty two degrees Twaddell) fifty five and one-quarter,

paraphenylene diamin hydrochlorid five and one-half, ormic acid (ninety per cent.) fifty,

boracic acid fiftytwo, sodium chlorate fifty five, coppersulfid paste (twenty four per cent.) fifty. Water to bulk to one thousand parts. s i a In preparing the above mixtures the thickening agents should be made into a paste with part of the water and a little formic acid and boiled in the usual manner to form a thickening. The anilin, the acids and the salts of .the bases may then'be added to the warm thickening and dissolved; then cool .and add the sodium chlorate in solution.

The copper salt should only be added immediately before use.

Of the mixtures of the above Examples Nos. 2, 4, 7 and 8 are intended for printing,

Nos. 1, 3, 5 and 6 for paddingmr otherwise impregnating fabrics. The fa rics are then dried and the black develo ed by steaming in a short steamer or an in ager of the Mather & Platt type.

What I claim as my invention and desire to secure by Letters Patent of the United States is-:--

1. A process of producing black upon vegetable textile fibers which consists in impregnating the fiber with a solution comprising anilin, strong mineralacid, formic acid, thickening, boracic acid, chlorates of A the alkali metals, paraphenylenediamin and with such mixtures by any then drying the impregnated fiber and developing by steaming in an anilin a er.

2. A process of producing blac ing anilin, strong mineral acid, formic acid, thickening, boracic acid and phosphoric acid, chlorates of the alkali metals, paraphenylenediamin and a copper salt, impregnating the textile fibers with such mixtures by any known process, then drying the impregnated fiber and developing by steaming in an anilin ager.

3. A dyeing solution comprising the following components in the proportions by weight as stated, starch thirty five, gum dragon mucilage one hundred and fifty, anilin seventy four and onequarter, hydrochloric acid (thirty two degrees Twaddell) twenty four and three-quarters, anilin salt 27% paraphenylenediamin hydrochlorid three and one-quarter, formic acid (ninety per cent.) ninety, lactic acid (thirty per cent.)

forty eight, boracic acid forty, sodium chlorate fifty two, copper chlorid eight and onequarter, and water to bulk to one thousand parts by volume.

4. A process of producing black upon upon vegetable textile fibers which consists in impregnatingthe fiber with a solution compris- I enzene series other than aminodiphenylamin compounds, strong mineral acid, formic acid, thickenin boracic acid, chlorates of the alkali meta s, paraphenylenediamin and a copper salt, impregnating the vegetable textile fibers with such mixtures by any known process, then drying the impregnated fiber and developing by steaming in an anilin ager.

5. A process of producing black upon vegetable textile fibers which consists in i1 npregnating the fiber with a solution comprising a plurality of primary amins of the benzene series other than aminodiphenylannn compounds, strong mineral acid, formic ac d, thickening, boracic acid and phosphoric acid, chlorates of the alkali metals, paraphenylenediamin and a copper salt, impregnating the vegetable textile fibers with such mixtures by any known process, then drylng the impregnated fiber and developing by steaming in an anilin ager.

In testimony whereof I have signed my.

name to this specification in the presence of two subscribing witnesses.

' EMILE AUGUSTE FOURNEAUX.

Witnesses:

S. W. GILLETT, HERBERT ROWLAND ABBEY. 

